Sulfur dyestuffs



Patented Nov. 17, 1931 UNITED STATES E T OFFICE FRIEDRICH MUTE, or ELBEZRFELID, GERMANY, assrenon TQ ENERALANILINE worms, me, on NEW YORK, N. Y., A CORPORATION or DELAWARE SULFUR n'znsrurrs I No Drawing. Application filed lJecember 9, 1929, Serial No. 412,937, and in Germany September 15, 1927.

The present invention relates to sulfur dyestuffs dyeing violet to green shades, which dyes are obtainable byreacting with sulfur upon a compound ofthe probable general formula G GHQ...

wherein A and B stand jointly for the group- 2) 2) 4* or D and E stand for hydrogen or ]O1Iltly for the grouping CH=CHCI-I= CH-'- or hydrogen or chlorine and It stands for hydrogen, alkyl, aralkyl or aryl. v

In my copending application Ser. No. 407,007, filed November 13, 1927, continuat on in part of Ser. No. 252,680, filed February 7th, 1928 I have described that compounds of the probable general formula:

wherein A, B, D, E and R have'the same meaning as in the above formula, will produce compounds having in their leuco form the first probable general formula, when caused to be reacted upon by p-aminophenols,

quinone-halogenimides or p-nitrosophenols according to the conditions usually employed tions of the leuco indophenols are easily reoxidized, for instance by action of atmos-1 pheric oxygen, to the corresponding indophenols. 5 7

N ow I have found that by submittin'g these novel indophenolic compoundsortheir leuco derivatives to: a sulfur fusion novel sulfur dyestuffs are produced. The products obtained in both cases are substantially identical; fwhenflusing the indophenolic com pounds, these arepresumably primarily reduced to the leuco indophenolic compounds in the sulfur melt. I wish it therefore to be understood that the term indophenolic compound is used herein as generic for both the indophenolic compounds and their leuco derivatives.

The conditions of the sulfur fusion can be varied within wide limits without. departing from the spiritof my invention. I, prefer, however, to use, an alcoholic e polysulfide fusion. A

My novel sulfurdyestufis are in the dry state dark violet to black powders, they are soluble in ,sodium sulfide solutions, from which cotton is dyed violet to green shades exceedingly fast to light and boiling. They "can also be reduced to form hydrosulfite vats, from which cotton is dyed in similar shades.

The following example will illustrate my A inventionwithout limiting it thereto:

E wampZe.- 280 parts by weight of the leuco indophenol from hexahydrocarbazole and para-aminoph enol having most probably the general formula; f A

are melted for about 'hours at 150160 C. with 690 parts by weight of calcined sodium sulfide, 830 parts by weight of sulfur and 1200 parts by weight of alcohol of 95%.

The alcohol is then-distilled off with the addition of water and thedyestuif which separates'is filtered. The residue is treated with suitable organic solvents dissolving sulfur or freed from sulfurby means of the exactly calculated quantity of sodium sulfide, the res idue is then washed and dried. The dyestuff forms in the dry state a blueish black powder, insoluble in organic solvents. It dyes cotton from a-sodium sulfide bath in blueish violet shades. Thedyeings are very fast to light and boiling.

The following table indicates the starting materials and shades of some othersulfur dyestuffs falling within the scope of my invention:

(6 hexahydrocarbazole) (4 hydroxy 3', 5 dichloro- V I phenyl) -amine CH: 2H5

(6 N ethyl hexahydro carbazole) (4' hydroxyphenyD-amine (6 N phenyl hexahydro carbazole) (4 hydroxyphenyl)-amine t CH V I (5-tetrahydropentindole)-(-1'-hydroxyphenyl)-an1ine [6 (7 8 tetrahydronaphtho-hexahydrocarbazole)1-(4hydroxyphenyl) -amine V NH H H bl "h 111s reen v H CH 7 a OH H [6-(7, S-naphtho-hexahydro-carbazole)]-4-hydroxypheny1)- V amine (preferably in presence of copper or its salts sulfate, cuprous sulfid lhis application is a continuation in part i of my application Ser. No.7303,111, filed August 30, 1928. .7

5 o1 a v 3 p HO NH- H H: i

blueish violet i 5' H H! j .g 01 I i N I l g.

I OH .v H

, V w v VCH1\ V i H0 ran-K T411 on: (1: blue g i H H: Y a k v t 4' 1] V -no-ONH n vv 7 CH1 violet 5 6 JKH V N 7 CH2 6 v clan-on 1 HO'NH n H CH; blueish violet as cuprous I claim:

1. New sulfur dyestuifs which in the dry state form violet to black powders, dyeing cotton from a sodium sulfide bath violet to green shades particularly fast to light and boiling, which are substantiallyddentical with the products obtainable by submitting to'a polysulfide' fusion, a compound having in j its le co f rm h np obab general formula:

product obtainable submitting the compound of the probableiormula:

NV on to a polysulfide fusion I "3. A new sulfur dyestufi" dyeing cotton from a sodium sulfide bath bluish-violet shades particularly fast to light and boiling, which is substantially identical with the product obtainable by submitting thecoiripound of the probable formula:

i D Oj cm H CH/ to a polysulfide fusion.

4. A new sulfur dyestuif dyeing cotton from a; sodium sulfide bath blue shades par ticularly fast to light and boiling, which is substantially identical with the product obtainable by submitting the compound of the probable formula:

HO NH S XHI O ()7; in.

to a polysulfide fusion.

In testimony whereof, I aflix my signature.

FRIEDRICH MUTH. 

